WO2005003753A1 - Accelerateurs de remineralisation - Google Patents

Accelerateurs de remineralisation Download PDF

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Publication number
WO2005003753A1
WO2005003753A1 PCT/JP2004/009443 JP2004009443W WO2005003753A1 WO 2005003753 A1 WO2005003753 A1 WO 2005003753A1 JP 2004009443 W JP2004009443 W JP 2004009443W WO 2005003753 A1 WO2005003753 A1 WO 2005003753A1
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WIPO (PCT)
Prior art keywords
phosphate
remineralization
starch
reaction
hydroxyapatite
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PCT/JP2004/009443
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English (en)
Japanese (ja)
Inventor
Reiichiro Sakamoto
Yoshikazu Sunada
Toshiyuki Kimura
Nobuo Uotsu
Akiko Koseki
Yuko Suda
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Oji Paper Co., Ltd.
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Priority to JP2005511365A priority Critical patent/JP4403140B2/ja
Publication of WO2005003753A1 publication Critical patent/WO2005003753A1/fr

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/163—Sugars; Polysaccharides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/26—Compounds containing phosphorus
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/212—Starch; Modified starch; Starch derivatives, e.g. esters or ethers
    • A23L29/219—Chemically modified starch; Reaction or complexation products of starch with other chemicals
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
    • A23L29/35—Degradation products of starch, e.g. hydrolysates, dextrins; Enzymatically modified starches
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/16—Inorganic salts, minerals or trace elements

Definitions

  • the present invention relates to a phenomenon in which water-soluble calcium phosphate coexisting in the presence of crystalline calcium phosphate is deposited on crystalline calcium phosphate, that is, relime having an effect of promoting a remineralization phenomenon of teeth.
  • the present invention relates to a chemical accelerator.
  • the remineralization accelerator of the present invention is used in fields such as foods, beverages, seasonings, taste improvers, oral hygiene agents, detergents, metal supplements, metal absorption enhancers, cosmetics, feed, and fertilizers. Things.
  • the present invention provides a method for producing a composition comprising a phosphate starch, a maltodextrin phosphate (PMD), an oligosaccharide phosphate (PS) having a remineralization promoting action, and salts thereof. Furthermore, the present invention relates to a method for producing a composition containing reduced maltodextrin phosphate, reduced phosphate oligosaccharide, and salts thereof.
  • PMD maltodextrin phosphate
  • PS oligosaccharide phosphate
  • Patent Document 1 PMDs and POSs having high Ca (calcium) solubilizing activity, and methods for producing them.
  • Patent Document 2 discloses a polyvalent metal salt composition of PMD or PS and a method for producing the same. These inventions relate to PMD and P ⁇ S which have the effect of maintaining poorly water-soluble calcium phosphate water-soluble.
  • a compound having a polymerization degree of dextrose of 10 or less which is a polysaccharide composed of dextrose having glucose 1,4 and d_1,6 bonds, is referred to as maltodextrin (MD). It is called oligosaccharide ( ⁇ S).
  • Patent Document 3 a composition having an anti-corrosion function of POS obtained from potato starch.
  • foods and drinks containing POS obtained from potato starch as a calcium enhancer are disclosed in Patent Document 3, and Patent Document 5 further discloses foods and drinks containing POS obtained from potato starch as a taste-improving agent.
  • the pile caries function includes both a caries prevention function and a caries treatment function, and (1) has a pH buffering action and is caused by an acid produced by oral bacteria. It has the ability to suppress pH drop. (2) It has the ability to suppress the formation of insoluble glucan produced by oral bacteria. (3) It has the ability to promote remineralization of teeth with initial caries. It means to have at least one of the following.
  • P ⁇ S and their sugar alcohols include acidic carbohydrates (oligogalataturonic acid, chondroitin sulfate, chondroitin sulfate oligosaccharide, glucose-1-6-phosphate), organic acids (tartaric acid) Citric acid, malic acid, lactic acid, fumaric acid, maleic acid), nucleic acids (phosphate esters of various nucleosides or nucleotides), amino acids and the like.
  • Patent Document 8 describes that notinite promotes remineralization of teeth.
  • Patent Document 9 describes that xylitol, mannitol, galactitol, and inositol promote tooth remineralization.
  • the effective concentration of these oligosaccharides and sugar alcohols to promote remineralization is several percent. Therefore, it can be said that the fact that the above-mentioned potato starch-derived POS exerts its effectiveness at a concentration as low as 0.2% is a very advantageous feature in terms of use in foods and the like.
  • POS derived from potato starch is composed of a group of oligosaccharides in which one phosphate group is bonded to three to five glucoses having ⁇ -1,4 linkages. This is a mixed composition of oligosaccharides in which two phosphate groups are bonded to two or eight glucoses with 1,4 linkages, and has a very low Ca solubilizing activity even though the phosphorus content is as high as 3% or more.
  • a starch such as a-amylase is used as a raw material by using a phosphate starch obtained by mixing phosphate with starch and roasting.
  • PMD and POS produced by hydrolysis with a degrading enzyme have a low bound phosphorus of around 2%, It has extremely high Ca solubilizing activity.
  • PMD and POS obtained from chemically prepared phosphate starch and POS obtained from natural potato starch have a considerable difference in the function of maintaining Ca solubility.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 11-255803
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2002-145893
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2002-325556
  • Patent Document 4 JP 2002-253170 A
  • Patent Document 5 JP-A-2002-253164
  • Patent Document 6 JP-A-8-104696
  • Patent Document 7 Japanese Patent Application Laid-Open No. 2002-325557
  • Patent Document 8 JP-A-2000-247852
  • Patent Document 9 JP-A-11-12143
  • POS derived from potato starch with bound phosphorus of 3.6% has an excellent remineralization promoting effect, whereas 1.8% of bound phosphorus obtained from chemically prepared phosphoric acid starch. PMD has no remineralization promoting effect.
  • POS derived from potato starch with bound phosphorus of 3.6% contains a large amount of soluble Ca in a reaction system in which hydroxyapatite does not exist, and the amount of soluble Ca decreases when hydroxyapatite is present. This As described above, a large difference in soluble Ca leads to an increase in Ca deposition on hydroxyapatite.
  • the measurement conditions of the remineralization test were improved, and a new remineralization acceleration evaluation method was established using the rate of Ca deposition on crystalline hydroxyapatite as an evaluation criterion.
  • a composition containing PMD and POS which has a remineralization promoting effect at an extremely lower concentration than POS derived from potato starch.
  • the remineralization promotion evaluation method of the present invention has found that substances such as organic acids, monosaccharides, oligosaccharides, and sugar alcohols exhibit a remineralization promotion effect in a certain concentration range.
  • the present invention relates to a substance or composition that exhibits a Ca solubilizing action and a remineralization promoting action at an extremely low concentration, and has a function of maintaining metal ions such as Ca in a soluble state, and an initial tooth sac.
  • the present invention includes the following inventions.
  • Buffer solution pH 7.0
  • KHPO solution water
  • reaction is performed in the same sample with the same amount of added calorie as in the case of the reaction without addition of hydroxyapatite in (ii), and the concentration of soluble calcium in the reaction solution is measured.
  • Calcium solubilization rate (%) [solubility of supernatant of reaction solution without hydroxyapatite addition] calcium / calcium added to reaction solution x 100
  • a sample solution is prepared by dissolving the composition in water and adjusting the pH to 6.5-7.0 with dilute NaOH solution or dilute HC1 solution.
  • the obtained sample solution is used on the day of preparation. Hydroxyapatite-free reaction and hydroxyapatite-added reaction of the same sample and the same amount are performed simultaneously.
  • all water uses purified water (water purified to an electric resistance of 1 ⁇ S or less).
  • the sample solution containing the obtained composition (0.002 mg-50 mg) is added sequentially to make a total volume of 8 mL. 36 ⁇ 0.3 of the vial containing the sample mixture obtained. Leave the sample in the C bath at least 10 minutes, and adjust the pH of the sample mixture to 7.00 ⁇ 0.02. The volume of dilute NaOH solution or diluted HC1 solution used for pH adjustment should be within 100 ⁇ L. After the pH adjustment, the sample mixture is returned to the thermostat and allowed to stand for at least 10 minutes. Then at 36 ⁇ 0.3 ° C pH 1 mL of water into the sample mixture adjusted to 7000 ⁇ 0.02
  • a hydroxyapatite suspension is prepared by previously suspending hydroxyapatite (for example, Hydroxyapatite type 1 manufactured by Sigma-Aldrich Co.) in water at a concentration of 5 mg ZmL.
  • hydroxyapatite for example, Hydroxyapatite type 1 manufactured by Sigma-Aldrich Co.
  • CaCl 3
  • Calcium solubilization rate (%) [Solubility of supernatant of reaction solution without addition of hydroxyapatite, calcium (ppm) / calcium added to reaction solution (ppm)] X 100
  • the ratio of this to the hydroxyapatite added to the reaction solution is set as the calcium deposition rate, and is calculated by the following equation.
  • Calcium deposition rate (%) ⁇ [solubility of supernatant of reaction solution without addition of hydroxyapatite lucidum (ppm)-soluble calcium of reaction supernatant of solution after addition of hydroxyapatite (ppm)] / added to reaction solution Hydroxyapatite (500ppm) ⁇ X 100
  • a composition containing at least one organic acid wherein the amount of the composition added in the remineralization test measurement method described in (2) is at least one of OO lmg-200 mg.
  • a remineralization accelerator which has an action of causing a calcium deposition rate to be 5% or more, preferably 10% or more.
  • composition containing at least one organic acid wherein the CaCl concentration in both reactions of the remineralization test measurement method described in (2) is 5 mM and the KH PO concentration is 3 mM.
  • a remineralization accelerator having an effect of increasing the calcium deposition rate to 5% or more, preferably 10% or more when the amount of the composition is at least 5 mg or 400 mg under the conditions.
  • a composition comprising at least one member selected from the group consisting of monosaccharides, oligosaccharides and sugar alcohols, wherein the composition according to the remineralization test measurement method described in (2) above is used.
  • Carohydrate content power OOmg A remineralization accelerator that has an action of increasing the calcium deposition rate to 5% or more, and preferably 10% or more, when the shear force is at least 100 mg.
  • a remineralization accelerator having an action of achieving a calcium deposition rate of 5% or more, preferably 10% or more when the amount of the composition added is at least 0.02 mg to 100 mg.
  • a composition comprising at least one selected from the group consisting of sugars and sugar alcohols, wherein the amount of the composition added is at least 0.02 mg lOOOO mg in the remineralization test measurement method described in (2) above.
  • a remineralization accelerator that has a calcium deposition rate of 5% or more, preferably 10% or more at the time of shear force.
  • a composition comprising a CaCl concentration of 10-15 mM and a KHPO concentration of 60% of CaCl concentration in both reactions of the remineralization test measurement method described in (2) above.
  • the amount of the composition added is as low as 0.02 mg—100 mg
  • a remineralization accelerator having an action of increasing the calcium deposition rate to 5% or more, preferably 10% or more.
  • a food, beverage, seasoning, taste improving agent, or oral cavity comprising at least one remineralization promoter according to any one of the above (2) to (14) Sanitizers, detergents, metal supplements, metal absorption enhancers, cosmetics, feed or fertilizers.
  • a mixture of reduced maltodextrin and / or reduced oligosaccharide produced by hydrogenating maltodextrin and / or oligosaccharide is mixed with phosphoric acid and Z or a phosphate, followed by roasting.
  • a composition comprising at least one of the obtained reduced maltodextrin phosphate, reduced phosphate oligosaccharide and salts thereof.
  • the present invention has an effect of depositing water-soluble calcium phosphate on crystals when crystalline calcium phosphate is present that only maintains the solubility of a metal salt such as calcium phosphate that cannot exhibit physiological effects due to poor water solubility. That is, the present invention provides a composition having an action of promoting remineralization. Search for remineralization promoting substances based on the Ca solubilization rate and Ca deposition rate by the newly set remineralization test method, and effectively use phosphate starch, PMD, POS, reduced PMD, reduced POS, organic acids, saccharides, etc. Substance found.
  • composition of the present invention exhibiting a remineralization promoting action includes foods, beverages, seasonings, taste improvers, oral hygiene agents, detergents, metal supplements, metal absorption promoters, cosmetics, feeds, fertilizers, and the like. It is used in a wide range of fields. BEST MODE FOR CARRYING OUT THE INVENTION
  • the first important function is to maintain calcium phosphate soluble.
  • Patent Document 1 Japanese Patent Application Laid-Open No. H11-255803
  • the present inventors have set a Ca solubilizing activity measurement method as a function of maintaining phosphoric acid lucidum soluble, and POS, which exhibits extremely high Ca solubilizing activity, Disclosure of PMD.
  • the second important function is the remineralization of calcium phosphate, which is deposited on calcium phosphate crystals, such as tooth crystal components.
  • Patent Document 7 Japanese Patent Application Laid-Open No. 2002-325557 discloses a method for simply measuring the remineralization action.
  • the remineralization phenomenon is described as follows: (1) Calcium (Ca) ions and phosphate ions, which are the constituent components, are supplied to the demineralization part. (2) The supplied Ca ions and phosphate ions are used for enamel crystal growth in the demineralized part.
  • the remineralization promoting substance is a substance that promotes the crystal growth of hydroxyapatite, which is a crystal component of teeth, while suppressing the insolubilization of Ca and phosphoric acid under neutral conditions.
  • a simple remineralization test system applying such a mechanism of remineralization is (A) a step of promoting a Ca precipitation reaction from a solution containing phosphoric acid, Ca and a sample in the presence of tooth components. (B) a step of measuring the Ca concentration or the amount of Ca precipitated in the solution after the precipitation reaction. (C) a step of promoting a Ca precipitation reaction from the solution in the absence of the tooth component. (D) a step of measuring the Ca concentration in the solution or the amount of generated Ca precipitate after the precipitation reaction in the absence of the tooth component. (E) Step of comparing the Ca concentration or the amount of precipitate in steps (B) and (D). It is stated that crystalline hydroxyapatite can be used as a tooth component.
  • reaction solution when the reaction solution was prepared, it was placed in a constant temperature bath at 37 ° C to adjust the temperature so that the reaction could be started at 37 ° C from the beginning of the reaction.
  • the calcium solubilization rate in the absence of apatite was greatly reduced, and the remineralization rate was reduced.
  • the remineralization rate was 55% under the conventional measurement conditions, but decreased to only 5%. .
  • the sample mixture was allowed to stand for at least 10 minutes in a constant temperature bath, and then the pH of the sample mixture was adjusted to 7.00 ⁇ 0.02. Again, the mixture was allowed to stand still for at least 10 minutes in the thermostat, and then the hydroxyapatite-containing reaction system was charged with the hydroxyapatite suspension, and the CaCl solution was immediately charged to start the reaction.
  • the remineralization rates at the respective temperatures of 35, 36, and 37 ° C with the addition of 20 mg of the above-mentioned potato starch-derived POS were 70%, 67%, and 5%.
  • a large difference in remineralization rate was observed between 36 ° C and 37 ° C, which resolved questions about the reproducibility of the measurement results.
  • the concentration of phosphoric acid contained in saliva is about 3 mM, which is higher than the Ca concentration.
  • Ca / P 5/3
  • CaZP molar ratio approaching 5/3 become.
  • what is important here is to maintain a high remineralization rate when the Ca concentration is between 3 mM and 5 mM.
  • the remineralization rate can be compared with the increase or decrease at the same Ca concentration. If the Ca concentration changes, the comparison becomes difficult. That is, when the Ca concentration is high, the Ca deposition rate may be higher than when the Ca concentration is low, even though the remineralization rate is low. Therefore, it was decided to evaluate the remineralization promoting effect by comparing the Ca deposition rate.
  • the trigger of the present invention is that, as described above, POS derived from potato starch and having a bond of 3.6% by weight has an excellent remineralization promoting effect, whereas chemically prepared phosphate PMD of 1.8% by weight of the bond obtained from starch had no remineralization promoting effect.
  • POS derived from potato starch showed a high soluble Ca concentration in a reaction system without hydroxyapatite, and a low soluble Ca concentration in a reaction system with hydroxyapatite. And the remineralization rate increases.
  • the binding P of natural potato starch is less than 0.1% by weight, and the average binding P of potato starch used as a saccharification raw material is about 0.05% by weight.
  • Phosphate starch preparation conditions were changed to produce phosphate starch with less than 1% by weight of bound P and degraded with a-amylase to produce various PMDs with different bound phosphorus.
  • POS derived from potato starch of 3.6% by weight has a remineralization rate of 67% and a Ca deposition rate of 13% with the addition of 20mg.
  • 1 ⁇ 0 with a combined P of 0.23 wt% showed a Ca deposition rate of 10% even if the amount of addition was reduced to 0.02111 ⁇ .
  • the POS derived from potato starch maintains a Ca deposition rate of 13% or more from 2 mg to 0.5 mg of added calories, but the Ca deposition rate becomes 7% when 0.2 mg is added.
  • the Ca deposition rate with the addition of 0.1 mg was reduced to 5%, and the effect of promoting remineralization was not much exhibited.
  • PMD and POS prepared from phosphoric acid starch as raw materials show a 10-fold or more remineralization-promoting action despite the fact that the bound phosphorus is as small as 1/15. Became clear.
  • Patent Document 7 Japanese Patent Application Laid-Open No. 2002-325557
  • PMD derived from phosphate starch shows a strong remineralization-promoting action despite a low amount of bound phosphorus.Comparing the buffering capacity with the amount of added katu, which shows the same Ca deposition rate, PH7.
  • PMD derived from phosphoric acid starch shows a remineralization-promoting effect even at an extremely low concentration that cannot exhibit buffer capacity, and it seems that buffer capacity hardly functions under conditions that promote remineralization. It is.
  • Organic acids are caries-causing substances that dissolve teeth and have never been considered to have a remineralization-promoting effect.
  • Lactic acid is a metabolite produced by the breakdown of carbohydrates by microorganisms in the mouth, and is the most causative substance of caries.
  • Ca 3.0 mM
  • P l.8 mM
  • lOOmg of lactic acid showed an unexpectedly 14% Ca deposition rate.
  • PMD was prepared by preparing a starch containing more than 2% by weight of bound P36.
  • Organic acids expected as remineralization accelerators include, for example, citric acid, malic acid, tartaric acid, dalconic acid, fumaric acid, succinic acid, acetic acid, lactic acid, adipic acid, itaconic acid, phytic acid, Examples include benzoic acid, ascorbic acid, darcono delta ratatone, polyketoglutaric acid, and acidic amino acids.
  • These organic acids are used, for example, as alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, ammonium salts, iron salts, zinc salts, copper salts and aluminum salts. You can also.
  • the present inventors have found a monosaccharide, an oligosaccharide, and a sugar alcohol having a remineralization promoting action by a new remineralization evaluation method.
  • carbohydrates and xylitol having a remineralizing action have a synergistic action with the PMD composition.
  • Addition of lOOmg xylitol under Ca 3mM, the ability to show 6% Ca deposition rate.
  • Add only 0.2mg of PMD derived from phosphoric acid starch (binding? 0.23% by weight). Showed a high value of 18%.
  • Monosaccharides expected as remineralization accelerators include, for example, glucose, fructose, mannose, galactose, talose, sonorebose, tagatose, deoxygnoleose, psicose, fucose, rhamnose, arose, anorethrose, and growth. , Idose, xylose, arabinose, ribose, deoxyribose, lyxose and the like.
  • Oligosaccharides expected as remineralization promoters include, for example, syrup, sucrose, palatinose, cellobiose, xylobiose, melibiose, chitobiose, kichibiose, and latte.
  • Sugar alcohols expected as remineralization accelerators include, for example, xylitol, sorbitole, maltitol, palatinit, reduced starch syrup, erythritole, xylitoleone, mannitol, galactitol, arabinitol, ratatitol, palatinit, Examples include ribitole, tretone, aritonore, isomaltitol, inositol, queritol, inosose, reduced starch saccharified product, and the like.
  • the Ca concentration in saliva shows a 9% Ca deposition rate
  • Patent Document 1 JP-A-11-255803 PMDs and POSs having excellent ability to maintain calcium phosphate in a soluble state.
  • the present invention relates to a remineralization promoting action that could not be predicted from the disclosure of Patent Document 1, and it is limited that a substance having high Ca solubilizing activity is not necessarily excellent in remineralization promoting action. I found nothing.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2002-325556 discloses a composition having an anti-corrosion function for P ⁇ S derived from potato starch.
  • Remineralized, extremely resistant to PMD and P ⁇ S, prepared from synthetic phosphate starch It has a calcifying effect and, unlike P ⁇ S derived from potato starch, shows a remineralizing effect at a concentration that shows almost no buffering effect, which is quite unexpected.
  • the newly developed remineralization evaluation method shows that organic acids, sugar alcohols, monosaccharides, and oligosaccharides also have effective concentrations that promote remineralization, and that PMD, POS, and remineralization are synergistic. The finding of an effect is an unknown phenomenon.
  • PMD and / or POS produced by allowing at least one kind of starch-degrading enzyme to act on a phosphoric acid starch obtained by phosphorylating starch, regardless of the raw material and the method for producing the same. All the compositions containing PMD and Z or POS, which show a Ca deposition rate of 5% or more, preferably 10% or more according to the remineralization test method of the present invention, are included in the scope of the present invention.
  • phosphoric acid starch with a Ca deposition rate of 5% or more, preferably 10% or more is also a target.
  • Phosphoric acid starch includes phosphoric acid starch in which phosphoric acid is ester-bonded and urea phosphoric acid starch. Is included.
  • Phosphoric acid starch, which is approved as a food additive, is sodium starch phosphate and contains 0.2 to 13% by weight of phosphorus as bound phosphorus, and the content of free phosphorus, that is, inorganic phosphorus, is total phosphorus (total phosphorus). ) Is specified as 20% or less.
  • the starch used as the raw material of the phosphoric acid starch can be any starch of plant origin, such as corn, potato, sweet potato, tapiochi, wheat, barley, and rice. Regardless of the origin, starch obtained by modifying starch by physical or chemical treatment can also be used. Furthermore, starch partially degraded by enzymatic treatment, that is, starch degradation products, can also be used as a raw material. Natural phosphoric acid starch having bound phosphorus such as potato starch can also be used as a raw material, but when synthetic phosphoric acid starch is used as a raw material, the method for synthesizing phosphoric acid starch is not particularly limited.
  • Phosphoric acid starch is usually produced by mixing a starch slurry with phosphoric acid and Z or a phosphate, followed by dehydration and drying-roasting, and adding a phosphoric acid and / or phosphate to a dehydrated starch cake.
  • a method of spraying and drying and roasting a solution, a method of mixing starch dry powder with a phosphoric acid and / or phosphate solution and drying and roasting are used.
  • urea phosphate ester starch can be synthesized by further adding urea as a chemical.
  • the slurry concentration is preferably 30 to 50% by weight from the viewpoint of maintaining uniform fluidity. Or 35-45% by weight.
  • Examples of phosphoric acid and / or phosphate include phosphoric acid, monosodium phosphate, disodium phosphate, trisodium phosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium acid pyrophosphate, and sodium hexametaphosphate.
  • Phosphate such as sodium phosphate such as sodium hexamethaphosphate
  • potassium phosphate such as monopotassium phosphate, dipotassium phosphate, potassium tripolyphosphate and potassium trimetaphosphate
  • monoammonium phosphate and diammonium phosphate A wide range of phosphates such as ammonium salts and phosphorus oxychloride can be used.
  • the amount of phosphoric acid and Z or phosphate added is 0.5-240% by weight, preferably 540% by weight, based on the weight of the starch which varies depending on the type.
  • urea phosphate starch urea-added kettle is required in addition to phosphate.
  • the amount of urea added is 0.5 240% by weight, preferably 560% by weight, based on the weight of the starch.
  • Acids and alkalis can be used to adjust the pH.
  • phosphoric acid can naturally be used, and in addition to phosphoric acid, hydrochloric acid, sulfuric acid, sulfurous acid and the like can be used.
  • alkali NaOH, KOH, Ca (OH) and the like can be used.
  • a mixture of starch and phosphoric acid and / or phosphate (including urea in the case of synthesis of urea phosphate starch) is desirably dried to remove water.
  • the roasting in the post-step of the phosphorylation reaction if there is a large amount of water, it becomes difficult to increase the phosphorylation rate (bound phosphorus / total phosphorus X 100), and the resulting phosphoric acid starch will be colored more. Occurs.
  • the roasting conditions for phosphorylating starch the higher the roasting temperature and the longer the roasting time, the greater the amount of bound phosphorus, but the color of the roasted product becomes reddish brown. Therefore, the roasting conditions are a temperature of 100-250 ° C, preferably 130-200 ° C, and a roasting time of 5 minutes 24 hours, preferably 10 minutes-14 hours. Heating is preferred.
  • the phosphate starch itself having a remineralization-promoting action in which the Ca deposition rate of the phosphate starch obtained by the above-described method is 5% or more is not only the target, but the phosphate starch itself is Even if it does not have the remineralization promoting action, in a food processing process using phosphoric acid starch as a raw material, the starch starch is decomposed by starch-degrading enzymes contained in other raw materials to exhibit remineralization promoting action. In such cases, the original phosphoric acid starch can be a remineralization accelerator.
  • phosphate starch added to foods is hydrolyzed by starch-degrading enzymes contained in human saliva to produce low molecular weight PMD and P ⁇ S, which promote remineralization.
  • the original phosphoric acid starch can be a remineralization accelerator.
  • a method in which starch is reduced in molecular weight and then phosphorylated may be employed. However, it was found that when the molecular weight of starch was reduced, coloring during heating and roasting was advanced, and decolorization and purification became difficult.
  • a phosphorylation reaction using a sugar alcohol mixture produced by hydrogenating a starch hydrolyzate such as a reduced starch hydrolyzate or reduced malt starch syrup will result in a reduced PMD with a high Ca deposition rate.
  • a starch hydrolyzate such as a reduced starch hydrolyzate or reduced malt starch syrup
  • / or a composition comprising reduced POS was found to be produced. Since the composition containing reduced PMD and / or reduced POS obtained by the roasting reaction has a low degree of coloration, it can be used as it is as it is as a commercial product. Becomes possible.
  • colored substances such as reduced PMD and reduced POS produced by phosphorylation using reduced dextrin (reduced starch decomposed product) or reduced malt starch syrup are produced by phosphorylation using starch as a raw material.
  • Less production of colored substances than phosphoric acid starch means that the load on the purification process is smaller than that of conventional reduced PMD or POS produced by hydrogenating PMD or POS obtained by enzymatic decomposition of phosphoric acid starch. This is a manufacturing method suitable for industrial production.
  • the generation of coloring substances is caused by the decomposition of some sugars in the roasting step of phosphorylation.
  • reduced PMD and reduced PS produced by linoxidation using the reduced dextrin and reduced starch syrup of the present invention as raw materials are the same as those of the conventional reduced PMD obtained by hydrogenating dextrin phosphate and oligosaccharide phosphate.
  • Reduced PS appears to be a phosphorylated saccharide with a novel composition that is strictly different.
  • the composition containing PMD and POS of the present invention can be obtained by decomposing the above-mentioned phosphate starch with human amylase to reduce the molecular weight. Because the viscosity decreases due to low molecular weight, food Applications for such applications are greatly expanded. Essentially, any enzyme used for degradation can be used as long as it is an ⁇ - amylase that randomly cuts starch, and two or more enzymes can naturally be used in combination.
  • heat-amylases in addition to heat-resistant liquefied heat-amylase frequently used for industrial starch decomposition (hereinafter also referred to as "liquefaction"), medium-temperature liquefied heat-amylase and saccharified heat-amylase are used.
  • CGTase Cyclomaltodextrin glucanotransferase
  • TVA a- ⁇ y ⁇ of Thermoactinomyces vulgaris
  • a liquefied heat-amylase having heat resistance is excellent in decomposing ability and dissolving power of starch.
  • the conditions under which the hair amylase acts on the phosphate starch vary depending on the type of the enzyme, but a commonly used enzyme operating temperature condition can be employed.
  • the enzyme used can be of any origin which is preferred for thermostable liquefied human amylase that works effectively at 80 110 ° C.
  • Termamyl 120 L and L / S (a product of Bacillus licheniformis, a product of Bacillus licheniformis, and Bacillus
  • neospitase PG2 manufactured by Nagase Seikagaku Kogyo, derived from Bacillus subtilis
  • kristase T manufactured by Daiwa Kasei, derived from Bacillus subtilis
  • Phosphoric acid starch as a substrate is prepared as a slurry having a concentration of 10 to 40% by weight, and calcium hydroxide and / or sodium hydroxide are added thereto, and usually adjusted to 116.0 to 6.3. Since thermostable ⁇ -amylase requires 50 ppm or more calcium 'ion as a stabilizer, calcium hydroxide is mainly used as an alkali for pH adjustment.
  • the amount of the enzyme to be added is 0.0001-0.5% by weight, preferably 0.01-0.2% by weight (vs. starch), which varies greatly depending on the enzyme used.
  • the reaction pH also depends on the enzyme used, usually between pH 4-7.
  • reaction reaction in order to prevent starch aging, the reaction start temperature after the addition of heat-amylase is increased to 100-110 ° C, and the mixture is treated under pressure for 215 minutes.
  • the enzymatic decomposition is carried out at a high temperature of 90-100 ° C for about 30 minutes to 5 hours.
  • the degradation of phosphate starch by heat-amylase does not necessarily require strict decomposition conditions such as 100 110C and pressurization.
  • Bound phosphorus Severe reaction conditions of 1 oo ° C or higher are not always necessary, though depending on the amount, since bound phosphorus plays a role in preventing starch aging.
  • high-temperature treatment of the decomposition reaction is preferable from the viewpoint of improving the filterability of the decomposition liquid and facilitating the operation.
  • phosphoric acid starch was collected to a final concentration of 10-40% by weight, 2.8% by weight of calcium chloride was added to the total volume of lZlOO, and the pH was adjusted to 6.3 with an lN_Na ⁇ H solution. I do. To this, add 0.1% by weight (to starch-bonded starch) of 120L of Termamill and transfer to a pressure vessel. After heating at 105 ° C for 5 minutes, continue liquefaction at 95 ° C for 1 hour.
  • the PMD composition obtained by treating phosphate starch with only sunflower amylase has a very strong remineralization promoting action, and can be obtained as a product if concentrated as it is.
  • the average degree of polymerization of a PMD composition obtained only by the treatment of phosphoric acid starch with amylase is 1050, which falls within the category of dextrin (degree of polymerization of 10 or more 100) rather than oligosaccharide (degree of polymerization of 10 or less). It has a degree of polymerization.
  • the viscosity of the product may increase, which may limit its use as a food.
  • one or more enzymes of various starch-degrading enzymes and glycosyltransferases, including ⁇ -amylase, and one or more enzymes of these enzymes An additional decomposition reaction (hereinafter, referred to as “saccharification reaction”) by an enzyme group obtained by adding ⁇ -dalcosidase to the enzyme can be performed.
  • starch-degrading enzymes such as dalcoamylase, -amylase, and saccharified ⁇ -amylase are recommended as highly effective enzymes for lowering the degree of polymerization of the oligosaccharide composition.
  • gnorecoamylase is mainly used for the additional decomposition for promoting the reduction of molecular weight, and furthermore, pullulanase and human amylase which are debranching enzymes are simultaneously acted on.
  • Patent Document 1 by the present inventors, after treatment with heat-resistant liquefied l-amylase, dextrozyme (manufactured by Novozyms Japan) which is a mixed enzyme preparation of dalcoamylase and pullulanase was used. To reduce the molecular weight. The PMD composition obtained by decomposing the synthesized phosphate starch with liquefied heat-amylase is further added. If you want to understand, Dalcoamylase sales enzyme agent AMG (Novosims Japan,
  • BBA (manufactured by Dienencore, derived from barley), which is a commercial enzyme for amylase, is used.
  • the average degree of polymerization of the POS composition obtained by additional decomposition with dalcoamylase was 114, and the average degree of polymerization of the POS composition obtained by additional decomposition with ⁇ -amylase was 418. .
  • the conditions for the additional degradation reaction by the starch-degrading enzyme vary greatly depending on the type of enzyme, but usually the reaction temperature is 20 70 ° C, the pH is 417, the degradation (saccharification) time is 0.5 96 hours, and the amount of enzyme added Is 0.0001 1% by weight based on the solid content of the raw material.
  • the enzyme used in the additional decomposition reaction can be used at the same time as the liquefied hermylase treatment used in the first decomposition.
  • the enzymatic degradation product of phosphoric acid starch includes insoluble substances such as added enzymes, aggregated proteins generated by a degradation reaction, and undegraded starch. Furthermore, unreacted inorganic phosphorus in the phosphorylation of starch and salts used for neutralization are also contained as impurities. Insoluble substances are removed by filtration or membrane treatment.To remove salts and inorganic phosphorus, desalination treatment by ion exchange resin treatment, nanofiltration (NF) membrane treatment, ion exchange membrane treatment, etc. is required. . By desalting a composition containing PMD and POS obtained by enzymatically decomposing phosphate starch, the ratio of inorganic phosphorus to total phosphorus can be reduced.
  • insoluble substances such as added enzymes, aggregated proteins generated by a degradation reaction, and undegraded starch. Furthermore, unreacted inorganic phosphorus in the phosphorylation of starch and salts used for neutralization are also contained as impurities. Insoluble substances are removed by filtration or
  • Phosphoric acid starch which is a food-added cauldron, can be added to food as it is.
  • ⁇ -amylase is converted to PMD and POS by being degraded by ⁇ -amylase.
  • heat-amylase derived from other raw materials during the processing process.
  • phosphate starch may be converted to PMD or P ⁇ S with high Ca deposition rates.
  • phosphate starch may be converted to PMD or POS by the action of salivary human amylase during chewing as a food even if there is no human amylase in the food.
  • Samples used in this test include compositions containing PMD and / or POS, phosphate starch, compositions containing reduced PMD and Z or reduced POS, organic acids, monosaccharides, oligosaccharides, sugar alcohols, etc.
  • a sample solution was prepared by dissolving each sample in water to form a 2% by weight solution.
  • high concentration sample solutions were also prepared and used as needed.
  • adjust the pH to 6.5 7.0 with a dilute Na ⁇ H solution or dilute HC1 solution to prepare a sample solution.
  • the obtained sample solution is used on the day of preparation.
  • the reaction of adding no hydroxyapatite and the reaction of adding hydroxyapatite in the same amount are performed simultaneously. All water used is purified water (water purified to an electric resistance of 1 ⁇ S or less, for example, demineralized distilled water regenerated with MILLI-Q Labo manufactured by MILLIPORE).
  • the Ca concentration is measured using a Ca measurement kit (for example, Calcium C Test Co., Ltd., manufactured by Wako Pure Chemical Industries) and displayed in ppm.
  • a Ca measurement kit for example, Calcium C Test Co., Ltd., manufactured by Wako Pure Chemical Industries
  • a hydroxyapatite suspension is prepared by previously suspending hydroxyapatite (Hydroxyapatite type 1 manufactured by Sigma-Aldrich Co.) at a concentration of 5 mg / mL in water. Prepare the standard reaction mixture composition in Table 1 as in the case of the reaction without hydroxyapatite. Reaction in the order of HEPES buffer (200 mM, pH 7.0), KH PO (18 mM) solution, water, and sample solution of each concentration
  • the Ca concentration is measured with a Ca measurement kit (eg, Wako Pure Chemical Calcium C Test Co., Ltd.) and expressed in ppm.
  • a Ca measurement kit eg, Wako Pure Chemical Calcium C Test Co., Ltd.
  • the concentration of soluble Ca in the solution after the completion of the reaction for 24 hours without adding hydroxyapatite was measured, and the Ca solubilization rate was calculated from the following equation.
  • Ca solubilization rate (%) [Soluble Ca (ppm) of supernatant of reaction solution without addition of hydroxyapatite / Ca (ppm) added to reaction solution] X 100
  • the soluble Ca concentration in the 24-hour reaction completed solution of hydroxyapatite-added kamut was subtracted from the soluble Ca concentration in the 24-hour reaction completed solution of hydroxyapatite-free kafun.
  • the value is assumed to be the amount of Ca deposited on hydroxyapatite, which is a crystal of calcium phosphate.
  • the ratio to roxyapatite was set as the Ca deposition rate, and was determined by the following equation.
  • Ca deposition rate (%) ⁇ [Soluble Ca (ppm) in supernatant of reaction solution without addition of hydroxyapatite-soluble Ca (ppm) in supernatant of reaction solution after addition of hydroxyapatite] / Hydrogen added to reaction solution Droxyanotite (500ppm) ⁇ X 100
  • the Ca deposition rate of the measurement sample is 5% or more, preferably 10% or more, it is determined that remineralization is promoted.
  • This criterion is set to be preferably 10% or more as the accelerating effect since the Ca deposition rate is about 9% at the Ca concentration of saliva as described above.
  • the Ca deposition rate drops to less than 2% if the substance is active, the Ca deposition rate is 5% at high Ca concentrations. . /.
  • the remineralization promoter of the present invention is used as a component of foods, beverages, seasonings, taste improvers, oral hygiene agents, detergents, metal supplements, metal absorption promoters, cosmetics, feeds, and fertilizers. be able to.
  • the Ca solubilization rate is further increased, and a soft drink containing a large amount of polyvalent metal salts such as Ca, Mg, and Fe can be produced.
  • polyvalent metal salts such as Ca, Mg, and Fe
  • the remineralization promoter of the present invention is used in foods, beverages, seasonings, taste improvers, oral hygiene agents, detergents, metal supplements, metal absorption promoters, cosmetics, feeds and fertilizers, Ca
  • the polyvalent metal salt can be maintained in a soluble state, that is, a state in which it can be used in a living body.
  • the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples.
  • the measurement of the bound phosphorus content and the measurement of the average degree of polymerization of the composition containing PMD and / or POS were performed by the following methods, respectively. I did it.
  • Phosphorus content was measured according to the method described in Starch'-Related Carbohydrate Experimental Method (Society Press Center, Michinori Nakamura et al.).
  • To measure the phosphorus content of the starch phosphate add 0.1% by weight of Termamyl (heat-resistant liquefied human-amylase) to the sample, heat decompose at 95 ° C for 15 minutes, cool with tap water, A homogeneous solution was prepared.
  • hydrochloric acid was added to the enzymatically decomposed solution to adjust the pH to 2, a sample solution was prepared, and phosphorus was measured by the Fiske-Subbarow method. In the case where turbidity was observed during color development, the supernatant was subjected to centrifugation (3000 rpm, 3 minutes) and the absorbance of the supernatant was measured.
  • the total phosphorus content was measured in the same manner as in the case of inorganic phosphorus measurement, and the sample solution adjusted to pH 2 was wet-ashed, and then phosphorus was measured in the same manner.
  • the bound phosphorus content (in each case, wt%, relative to the sample solids) was determined from the following equation.
  • Bound phosphorus content (total phosphorus content-inorganic phosphorus content)
  • the sugar content is measured in accordance with the method described in Experimental Methods for Starch and Related Carbohydrates (Academic Publishing Center, Michinori Nakamura et al.), And the average degree of polymerization of the composition containing PMD and / or POS is determined from total sugar / reducing sugar.
  • the sample solution adjusted to pH 2 was appropriately diluted, and the total sugar was measured by the phenol-sulfuric acid method (Dubois et al., 1956), and the reducing sugar was measured by the Somogyt Nelson method (Nelson, 1944).
  • the measured value was expressed in terms of glucose equivalent weight% (based on the solid content of the sample), and the average degree of polymerization was determined from the following equation.
  • Average degree of polymerization total sugar (% by weight) / reducing sugar (% by weight)
  • phosphate starch was hydrolyzed with a starch-degrading enzyme to prepare a low molecular weight PMD composition.
  • Collect 3 to 4 g of the obtained phosphoric acid starch dry at 105 ° C for 4 hours, allow to cool, precisely weigh 2 g of the dried sample, place it in a lOOmL pressure-resistant glass container, add 70 g of water, and mix uniformly. It was stirred until it became.
  • This 2.8 weight 0/0 of ImL of calcium chloride solution Ka ⁇ E the pH was adjusted to 6.3 with IN-NaO H solution.
  • the bound phosphorus content and the degree of polymerization of the obtained sugar composition were measured. Table 2 shows the results.
  • the average polymerization degree of each composition is about 10 S, and the sugar with phosphorus attached is less susceptible to decomposition than the sugar without phosphorus attached. Will be high. Therefore, the following composition contains almost no POS having a degree of polymerization of 10 or less and is mainly composed of PMD having a degree of polymerization of 11 or more, and is therefore referred to as a PMD composition.
  • the average degree of polymerization of the nine types of PMD compositions was around 150.
  • the original phosphate starch has a slightly lower solubilization rate of Ca.
  • the P ⁇ S composition and the PMD composition did not show any remineralization promoting action, but the action of promoting remineralization was observed at a certain concentration of many organic acids.
  • the organic acid required a larger amount of addition for the Ca deposition rate to be 10% or more.
  • High fructose liquid sugar and palatinose have high Ca solubility, especially high fructose liquid sugar is 600m More than 90% of the calcium phosphate was dissolved with the added amount of g.
  • Fructose-glucose liquid sugar, high-fructose liquid sugar, palatinose and sucrose show a remineralization-promoting effect, and in particular, high fructose liquid sugar has a Ca deposition rate of 15% even with the addition of 400 mg.
  • kristase manufactured by Daiwa Kasei Co., Ltd.
  • the liquefaction reaction was performed at 90 ° C for 1 hour. Next, the solution temperature was cooled to 60 ° C, and thereafter, saccharification reaction was performed at 60 ° C by adding 0.05% by weight (based on solid content) of poramylase (manufactured by Novozyms Japan, Whangamil). After 16 hours, the temperature was raised to 80 ° C and maintained for 2 hours to inactivate the enzyme.
  • poramylase manufactured by Novozyms Japan, Whangamil
  • the combination of the PMD composition and the organic acid showed a marked increase in remineralization promoting effect in all combinations tested. Lactic acid alone has a remineralization-promoting effect when added at lOOmg or more, but not when added at a dose of 50mg (Table 19).
  • Combining a PD of 0.23% by weight with a PMD composition the Ca deposition rate can be much higher than 10%. Adding only 0.2 mg of the PMD composition can reduce the Ca deposition rate to 25%. %.
  • Example 11 Water and potato starch were mixed to prepare 270 kg of a slurry having a starch concentration of 30% by weight, and the pH was adjusted to 6.3 by adding slaked lime. Next, 120 L of Tamamill was added to the jet tucker by adding 0.05% by weight to starch. After maintaining the cooking temperature at 105 ° C and the pressure at lkg / cm 2 (gage pressure), guide it to a high-temperature retention tower, hold it under pressure at 105 ° C for 5 minutes, and then transfer it to an aging tank. It was liquefied by holding at 95 ° C for 2 hours. After cooling the obtained liquefied liquid to 60 ° C., oxalic acid was added to adjust the pH to 4.5. The saccharification reaction was promoted by adding dextrozyme to starch at 0.1% by weight and maintaining the mixture at 60 ° C for 40 hours.
  • the obtained saccharified solution of potato starch was filtered with a filter press, and the clarified solution was passed through a decolorization tower filled with granular activated carbon to be decolorized.
  • the obtained sugar solution is converted into a strongly acidic cation exchange resin (LEVATIT S-100WS), a weakly basic anion exchange resin (LEVATIT MP64-WS), a strongly acidic cation exchange resin (LEVATIT SP-112WS), and a strongly basic anion exchange resin. (LEVACIT MP-600).
  • desalted water was passed through the resin tower to extrude the sugar solution.
  • the POS adsorbed on the anion exchange resin was eluted by passing a 4% by weight caustic soda solution heated to 40 ° C. through the weakly basic anion exchange resin. Effluent volume begins to recover from the 1.0 times the eluate fractions of the resin capacity, by recovering up to 1.7 times the resin volume, Natoriumu salt of 1 3 Rei_3 containing solids 13 wt% solution 3.513 ⁇ 4 (Average degree of polymerization 4, bound phosphorus 3.6%) was obtained.
  • the resulting phosphoric acid starch was dissolved at 20 weight 0/0 concentration shed - 0.1 wt% of Tamaminore 120L as amylase (vs. solids) was added, mosquitoes and CaCl As further Ca concentration of 50ppm ⁇ I got it.
  • the pH was adjusted to 6.0 with NaOH, and the mixture was liquefied at 95 ° C for 2 hours by steam heating.
  • the mixture was heated at 2 ° C. for 2 hours and filtered through a ceramic filter (pore size: 0.2 / i).
  • the filtrate was spray-dried to obtain 6.4 kg of a powdered POS calcium salt composition.
  • the bond P of the obtained POS calcium salt composition was 2.8% by weight, the inorganic P was 0.19% by weight, and the average degree of polymerization was 6.4.
  • a mixed solution of monosodium phosphate and disodium phosphate was added to the starch slurry to dissolve it, dried with a drum dryer and pulverized.
  • the obtained phosphoric acid starch (100 kg) was dissolved at a concentration of 20% by weight, and 120 L of terminol as a heat-amylase was added at 0.05% by weight (based on solid content), and CaCl was calored so that the Ca concentration became 50 ppm. Adjust the pH to 6.0 with NaOH, then heat to 90 ° C with steam heating.
  • a liquefaction reaction was performed for 2 hours. Then, in order to reduce the molecular weight, the solution was cooled down to 60 ° C and added with 0.05% by weight (to solid content) of force, ra-amylase (manufactured by Novozyms Japan) and saccharified at 60 ° C. The reaction was performed. Twenty hours later, Termal Mill 120 L was added in an amount of 0.02% by weight (based on solid content), and the temperature was raised to 80 ° C and maintained for 2 hours.
  • the reaction was stopped by adding 1% by weight (based on solid content) of powdered activated carbon, and the mixture was filtered through a ceramic filter (pore size: 0.2 /).
  • a ceramic filter pore size: 0.2 /.
  • 1000 kg of the obtained permeate was concentrated on a NF membrane (Nitto Denko NTR-7430) processor with a salt rejection of 30%. After concentrating with an evaporator, add NaOH to make ⁇ 6.0 Then, 47 kg of a powdered POS sodium salt composition was obtained.
  • a mixed solution of monosodium phosphate and disodium phosphate was added to the dried starch and dried with a flash dryer.
  • Dissolve 100 kg of the obtained phosphoric acid starch at a concentration of 20% by weight add 120 L of tamminole as a heat-amylase (0.03% by weight to solid content), and further add CaCl to bring the Ca concentration to 50 ppm. I got it. Adjust the pH to 6.3 with NaOH and adjust the temperature to 90 ° C with steam and calo heat.
  • the reaction was stopped by adding 1% by weight (based on solid content) of powdered activated carbon, and the mixture was filtered through a ceramic filter (pore size 0.2 /). Further, the mixture was concentrated by an evaporator and subjected to a spray dryer to obtain 75 kg of a powdery PMD sodium salt composition.
  • the resulting PMD composition had a binding P of 0.25% by weight, an inorganic P of 0.06% by weight, and an average degree of polymerization of 11.
  • the mixture was concentrated with an evaporator, and dried with a spray drier to obtain 85 kg of a calcium-sodium-containing PMD composition containing powder.
  • the binding P was 0.27% by weight
  • the inorganic P was 0.05% by weight
  • the average degree of polymerization was 12.
  • a mixed solution of monosodium phosphate and disodium phosphate was added to the dried starch and dried with a flash dryer.
  • 100 kg of the obtained phosphoric acid starch is dissolved at a concentration of 20% by weight, and klysase (manufactured by Daiwa Kasei) 0.05% by weight (based on solid content) is added as an ⁇ -amylase so that the Ca concentration becomes 50 ppm.
  • the reaction was stopped by adding 1% by weight (based on solid content) of powdered activated carbon, and the mixture was filtered through a ceramic filter (pore size: 0.2 ⁇ ). 900 kg of the obtained permeate was concentrated using a NF membrane (Nitto Denko NTR-7430) processor with a salt rejection of 30%. Further, the mixture was concentrated with an evaporator, and Na ⁇ H was added to adjust the pH to 6.0, followed by spraying to obtain 5 lkg of a powdery PMD sodium salt composition.
  • NF membrane Nito Denko NTR-7430
  • the obtained PMD composition had a binding P of 2.8% by weight, an inorganic P of 0.3% by weight, and an average degree of polymerization of 10%.
  • a remineralization test was performed under the conditions, and the Ca solubilization rate and Ca deposition rate were calculated. The results are shown in Table 41.
  • the present invention is used in the fields of foods, beverages, seasonings, taste improvers, oral hygiene agents, detergents, metal supplements, metal absorption promoters, cosmetics, feeds, and fertilizers.

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Abstract

L'invention concerne des substances ou des compositions présentant la fonction de maintenir des ions métalliques, tels que des ions Ca, à l'état soluble, ainsi qu'une fonction d'accélération de la reminéralisation et de réparation des caries dentaires à un stade précoce. Lesdites substances ou compositions sont utilisées dans des produits alimentaires, des boissons, des assaisonnements, des agents améliorant le goût, des produits d'hygiène buccale, des détergents, des fournisseurs de métaux, des accélérateurs d'absorption de métaux, des produits cosmétiques, des aliments pour animaux et des engrais. L'invention concerne en particulier un accélérateur de reminéralisation se présentant sous la forme d'une composition contenant au moins un élément choisi dans le groupe constitué par le phosphate d'amidon, le phosphate de maltodextrine, le phosphate réducteur de maltodextrine, le phosphate d'oligosaccharide, le phosphate réducteur d'oligosaccharide, des acides organiques et des saccharides. Ledit accélérateur exerce un rapport de calcipexie de 5 % ou supérieur, de préférence 10 % ou supérieur, dans une réaction de test de reminéralisation donnée. L'invention concerne encore des produits alimentaires, des boissons, des assaisonnements, des agents améliorant le goût, des produits d'hygiène buccale, des détergents, des fournisseurs de métaux, des accélérateurs d'absorption de métaux, des produits cosmétiques, des aliments pour animaux ou des engrais se caractérisant en ce qu'ils contiennent ledit accélérateur de reminéralisation.
PCT/JP2004/009443 2003-07-07 2004-07-02 Accelerateurs de remineralisation WO2005003753A1 (fr)

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JP2010215558A (ja) * 2009-03-17 2010-09-30 Lion Corp 歯の脱灰抑制剤及び口腔用組成物
JP2012131750A (ja) * 2010-12-24 2012-07-12 San-Ei Sucrochemical Co Ltd 歯牙エナメル質の再石灰化促進剤
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JP2015221821A (ja) * 2015-08-11 2015-12-10 サンエイ糖化株式会社 歯牙エナメル質の再石灰化促進剤
JP2019137645A (ja) * 2018-02-14 2019-08-22 王子ホールディングス株式会社 カルシウム溶解促進剤
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JP2006249316A (ja) * 2005-03-11 2006-09-21 Oji Paper Co Ltd リン酸澱粉の製造方法
JP2010215558A (ja) * 2009-03-17 2010-09-30 Lion Corp 歯の脱灰抑制剤及び口腔用組成物
JP2012131750A (ja) * 2010-12-24 2012-07-12 San-Ei Sucrochemical Co Ltd 歯牙エナメル質の再石灰化促進剤
FR3011466A1 (fr) * 2013-10-09 2015-04-10 Roquette Freres Utilisation d'un polyol dans la remineralisation de l'email
WO2015052447A1 (fr) * 2013-10-09 2015-04-16 Roquette Freres Utilisation d'un polyol dans la remineralisation de l'email
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JP2015221821A (ja) * 2015-08-11 2015-12-10 サンエイ糖化株式会社 歯牙エナメル質の再石灰化促進剤
JP2019137645A (ja) * 2018-02-14 2019-08-22 王子ホールディングス株式会社 カルシウム溶解促進剤
WO2019159914A1 (fr) * 2018-02-14 2019-08-22 王子ホールディングス株式会社 Accélérateur de dissolution du calcium
CN114289492A (zh) * 2021-12-29 2022-04-08 上海应用技术大学 磷酸盐土壤改良剂在农田固碳协同调控镉污染中的应用方法

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